skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: LDRD final report on new homogeneous catalysts for direct olefin epoxidation (LDRD 52591).

Abstract

This report summarizes our findings during the study of a novel homogeneous epoxidation catalyst system that uses molecular oxygen as the oxidant, a ''Holy Grail'' in catalysis. While olefins (alkenes) that do not contain allylic hydrogens can be epoxidized directly using heterogeneous catalysts, most olefins cannot, and so a general, atom-efficient route is desired. While most of the work performed on this LDRD has been on pincer complexes of late transition metals, we also scouted out metal/ligand combinations that were significantly different, and unfortunately, less successful. Most of the work reported here deals with phosphorus-ligated Pd hydrides [(PCP)Pd-H]. We have demonstrated that molecular oxygen gas can insert into the Pd-H bond, giving a structurally characterized Pd-OOH species. This species reacts with oxygen acceptors such as olefins to donate an oxygen atom, although in various levels of selectivity, and to generate a [(PCP)Pd-OH] molecule. We discovered that the active [(PCP)Pd-H] active catalyst can be regenerated by addition of either CO or hydrogen. The demonstration of each step of the catalytic cycle is quite significant. Extensions to the pincer-Pd chemistry by attaching a fluorinated tail to the pincer designed to be used in solvents with higher oxygen solubilities are also presented.

Authors:
 [1];  [1]; ; ; ; ;  [2];  [3];  [1]
  1. (University of Washington)
  2. (New Mexico Institute of Mining and Technology)
  3. (University of Washington)
Publication Date:
Research Org.:
Sandia National Laboratories
Sponsoring Org.:
USDOE
OSTI Identifier:
878587
Report Number(s):
SAND2005-6754
TRN: US200611%%342
DOE Contract Number:  
AC04-94AL85000
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
08 HYDROGEN; ALKENES; CATALYSIS; CATALYSTS; CHEMISTRY; HYDRIDES; HYDROGEN; OXYGEN; SOLVENTS; TRANSITION ELEMENTS; Alkenes.; Catalysts.; Oxygen-Analysis.

Citation Formats

Goldberg, Karen, Smythe, Nicole A., Moore, Joshua T., Stewart, Constantine A., Kemp, Richard Alan, Miller, James Edward, Kornienko, Alexander, Denney, Melanie C., and Cetto, Kara L.. LDRD final report on new homogeneous catalysts for direct olefin epoxidation (LDRD 52591).. United States: N. p., 2006. Web. doi:10.2172/878587.
Goldberg, Karen, Smythe, Nicole A., Moore, Joshua T., Stewart, Constantine A., Kemp, Richard Alan, Miller, James Edward, Kornienko, Alexander, Denney, Melanie C., & Cetto, Kara L.. LDRD final report on new homogeneous catalysts for direct olefin epoxidation (LDRD 52591).. United States. doi:10.2172/878587.
Goldberg, Karen, Smythe, Nicole A., Moore, Joshua T., Stewart, Constantine A., Kemp, Richard Alan, Miller, James Edward, Kornienko, Alexander, Denney, Melanie C., and Cetto, Kara L.. Wed . "LDRD final report on new homogeneous catalysts for direct olefin epoxidation (LDRD 52591).". United States. doi:10.2172/878587. https://www.osti.gov/servlets/purl/878587.
@article{osti_878587,
title = {LDRD final report on new homogeneous catalysts for direct olefin epoxidation (LDRD 52591).},
author = {Goldberg, Karen and Smythe, Nicole A. and Moore, Joshua T. and Stewart, Constantine A. and Kemp, Richard Alan and Miller, James Edward and Kornienko, Alexander and Denney, Melanie C. and Cetto, Kara L.},
abstractNote = {This report summarizes our findings during the study of a novel homogeneous epoxidation catalyst system that uses molecular oxygen as the oxidant, a ''Holy Grail'' in catalysis. While olefins (alkenes) that do not contain allylic hydrogens can be epoxidized directly using heterogeneous catalysts, most olefins cannot, and so a general, atom-efficient route is desired. While most of the work performed on this LDRD has been on pincer complexes of late transition metals, we also scouted out metal/ligand combinations that were significantly different, and unfortunately, less successful. Most of the work reported here deals with phosphorus-ligated Pd hydrides [(PCP)Pd-H]. We have demonstrated that molecular oxygen gas can insert into the Pd-H bond, giving a structurally characterized Pd-OOH species. This species reacts with oxygen acceptors such as olefins to donate an oxygen atom, although in various levels of selectivity, and to generate a [(PCP)Pd-OH] molecule. We discovered that the active [(PCP)Pd-H] active catalyst can be regenerated by addition of either CO or hydrogen. The demonstration of each step of the catalytic cycle is quite significant. Extensions to the pincer-Pd chemistry by attaching a fluorinated tail to the pincer designed to be used in solvents with higher oxygen solubilities are also presented.},
doi = {10.2172/878587},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Feb 01 00:00:00 EST 2006},
month = {Wed Feb 01 00:00:00 EST 2006}
}

Technical Report:

Save / Share: